JP2023524730A - Polyamide composition with modified impact resistance - Google Patents

Abstract

Described herein are polymer compositions (PC) comprising a polyamide (PA) and a reactive impact modifier. Polyamides (PA), as described in detail below, are semi-polyamides derived from the polycondensation of aliphatic diamines, bis(aminoalkyl)cyclohexanes, terephthalic acid, and optionally cyclohexanedicarboxylic acid. It is an aromatic polyamide. Surprisingly, a semi-aromatic polyamide derived from a cycloaliphatic diamine bis(aminoalkyl)cyclohexane or a specific combination of a cycloaliphatic diamine bis(aminoalkyl) cyclohexane and a cycloaliphatic dicarboxylic acid cyclohexanedicarboxylic acid can be prepared in an aqueous solution. polymer compositions with improved retention of mechanical properties (e.g. tensile and flexural strength) after aging in bis(aminoalkyl)cyclohexanes and similar polyamides without cyclohexanedicarboxylic acids ( PC). [Selection figure] None

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is subject to U.S. Provisional Patent Application No. 63/021,107 filed May 7, 2020 and European Patent Application No. 20185587.1 filed July 14, 2020. , both of which are incorporated herein by reference.

The present invention relates to polymer compositions containing polyamides and reactive impact modifiers that retain good mechanical properties after aging. The present invention also relates to methods of making the polymer compositions and articles incorporating the polymer compositions.

Conventional semi-aromatic polyamides are used in the manufacture of parts exposed to engine coolants and saline solutions. The high chemical resistance and desirable mechanical performance of these traditional semi-aromatic polyamides make them particularly suitable for engine coolant and saline solution environments. However, such articles are typically placed in high temperature environments, subjecting the articles to high temperatures. Over time, the mechanical performance of such articles can degrade to undesirable levels.

In one aspect, the present invention relates to a polymer composition (PC) comprising a polyamide (PA) and a reactive impact modifier (IM). Polyamide (PA) is a diamine component (A) containing 20 mol % to 95 mol % C ₄ -C ₁₂ aliphatic diamine and 5 mol % to 80 mol % bis(aminoalkyl)cyclohexane , the mole percentages of which are relative to the total number of moles of each diamine in the diamine component, the diamine component (A); wherein the mole percentages of these are relative to the total number of moles of each dicarboxylic acid in the dicarboxylic acid component; It is derived from the polycondensation of monomers. In some embodiments, the bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane. In some embodiments, the dicarboxylic acid component (B) is 1 mol% to 70 mol% of cyclohexanedicarboxylic acid, preferably 1,4-cyclohexanedicarboxylic acid, based on the total moles of each dicarboxylic acid in the dicarboxylic acid component. Contains acid.

In some embodiments, the reactive impact modifier (IM) is a maleic anhydride functionalized impact modifier. In some embodiments, the concentration of reactive impact modifier (IM) is from 1% to 20% by weight. In some embodiments, the polymer composition (PC) further comprises 5% to 70% by weight of a reinforcing agent, based on the total weight of the polymer composition. In some embodiments, the reinforcing agent is glass or carbon fiber, preferably glass fiber.

In some embodiments, the polymer composition (PC) has a tensile strength retention of at least 60% after aging in a 50:50 ethylene glycol:water solution at 130° C. for 1000 hours. In some embodiments, the polymer composition (PC) has a flexural strength retention of at least 85% after thermal aging for 1000 hours in a 26 wt% aqueous NaCl solution at 130°C.

In another aspect, the invention relates to an article comprising the polymer composition (PC), which article is an automotive component or a component for underground or subsea oil and gas.

Described herein are polymer compositions (PC) comprising a polyamide (PA) and a reactive impact modifier. Polyamides (PA), as described in detail below, are semi-polyamides derived from the polycondensation of aliphatic diamines, bis(aminoalkyl)cyclohexanes, terephthalic acid, and optionally cyclohexanedicarboxylic acid. It is an aromatic polyamide. Surprisingly, semi-aromatic polyamides derived from cycloaliphatic diamine bis(aminoalkyl) cyclohexanes or specific combinations of cycloaliphatic diamine bis(aminoalkyl) cyclohexanes and cycloaliphatic dicarboxylic acids cyclohexane dicarboxylic acids are produced in aqueous solutions. polymer compositions with improved retention of mechanical properties (e.g. tensile strength and flexural strength) after aging in bis(aminoalkyl)cyclohexanes and similar polyamides without cyclohexanedicarboxylic acids ( PC). For the sake of clarity, references herein to "aging" implicitly refer to thermal aging in aqueous solution. Due in part to improved retention of mechanical properties after aging, the polymer composition (PC) is desirably exposed to high temperatures during use and aqueous solutions (including but not limited to engine coolants and saline solutions, etc.) into articles designed to carry or store them. Further, the polymer composition (PC) can desirably be formulated into articles designed for use in underground oil recovery components and exposed to saline solutions.

In this application, any description, even if described in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the disclosure. Where an element or component is included in and/or selected from a recited list of elements or components, in related embodiments expressly contemplated in the present application, the component or component is individually or may be selected from the group consisting of any two or more of the specifically recited elements or components; Any element or component may be omitted from such lists; any recitation herein of numerical ranges by endpoints includes all numbers within the recited range, as well as the range endpoints and equivalents. It should be understood that

Unless specifically limited otherwise, the terms "alkyl" and derivative terms such as "alkoxy", "acyl" and "alkylthio", as used herein, include straight-chain, branched-chain and cyclic Including part. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl and cyclopropyl. Unless otherwise specifically stated, each alkyl and aryl group may be unsubstituted or halogen, hydroxy, sulfo, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ acyl, formyl , cyano, C ₆ -C ₁₅ aryloxy or C ₆ -C ₁₅ aryl, provided that the substituents are sterically compatible , provided that the chemical bonding and strain energy rules are satisfied. The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine, with fluorine being preferred.

The term "aryl" refers to phenyl, indanyl or naphthyl groups. Aryl groups may contain one or more alkyl groups, in which case they may also be referred to as "alkylaryl"; for example composed of a cycloaromatic group and two C ₁ -C ₆ groups (eg, methyl or ethyl). can be Aryl groups may also contain one or more heteroatoms such as N, O or S, in which case they may also be referred to as "heteroaryl"groups; these heteroaromatic rings may be fused to other aromatic systems. obtain. Such heteroaromatic rings include, but are not limited to furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl and triazinyl ring structures. Aryl or heteroaryl substituents are unsubstituted or halogen, hydroxy, C ₁ -C ₆ alkoxy, sulfo, C ₁ -C ₆ alkylthio, C ₁ -C ₆ acyl, formyl, cyano, C ₆ -C may be substituted with one or more substituents selected from, but not limited to, C ₆ -C ₁₅ aryloxy or C 6 _{-C 15} aryl, provided that the substituents are sterically compatible, chemical bond and strain energy provided that the rules of

As noted above, it has been surprisingly discovered that polymer compositions (PC) have improved retention of mechanical properties after aging in aqueous solutions at elevated temperatures. In some embodiments, the aqueous solution is an aqueous polyol solution or a saline solution. Polyols are organic compounds containing at least two hydroxyl groups. Polyols of interest herein include, but are not limited to, ethylene glycol, propylene glycol, and diethylene glycol. Typically, engine coolants utilize an aqueous polyol solution having a water to polyol (eg, ethylene glycol) weight ratio of 99.9/0.1 to 50:50. A saline solution refers to a solution comprising water and at least 3.5% by weight NaCl based on the total weight of water and NaCl. In some embodiments, the saline solution has a NaCl concentration of up to 26% by weight based on the total weight of water and NaCl. Mechanical property retention can be determined according to the following formula: 100*(X ₁ /X ₀ ), where X ₁ is the value of a given mechanical property after aging and X ₀ is the aging is the value of the mechanical properties before (eg during molding). Unless explicitly stated otherwise, aging in aqueous polyol as used herein means immersing the polymer composition (PC) in a 50:50 ethylene glycol:water solution at 130° C. for 1000 hours. refers to doing Similarly, unless explicitly stated otherwise, aging in saline solution as used herein means immersing the polymer composition (PC) in a 26 wt % NaCl aqueous solution at 130° C. for 1000 hours. point to

In some embodiments, the polymer composition (PC) has a tensile strength retention of at least 60%, at least 70% after aging in an aqueous polyol solution. In some embodiments, the polymer composition (PC) exhibits a tensile strength retention of 100% or less, 95% or less, 90% or less, 85% or less, or 80% or less after aging in an aqueous polyol solution. have. In some embodiments, the polymer composition (PC) is 60% to 100%, 60% to 95%, 60% to 90%, 60% to 85%, 60% to It has a tensile strength retention of 80%, 70%-100%, 70%-95%, 70%-90%, 70%-85%, or 70%-80%. In some embodiments, the polymer composition (PC) has a tensile strength of at least 120 MPa, at least 130 MPa, at least 140 MPa, or at least 150 MPa after aging in an aqueous polyol solution. In some embodiments, the polymer composition (PC) has a tensile strength of 190 MPa or less, 180 MPa or less, 170 MPa or less, or 160 MPa or less after aging in an aqueous polyol solution. In some embodiments, the polymer composition (PC) has a tensile strength of 120 MPa to 190 MPa, 130 MPa to 180 MPa, 150 MPa to 170 MPa, or 150 MPa to 160 MPa after aging in an aqueous polyol solution. Tensile strength can be measured as described in the Examples section.

In some embodiments, the polymer composition (PC) has a flexural strength retention of at least 85%, at least 90%, or at least 95% after aging in saline solution. In some embodiments, the polymer composition (PC) has a flexural strength retention of 105% or less, 100% or less, or 99% or less after aging in saline solution. In some embodiments, the polymer composition (PC) is 85% to 105%, 90% to 105%, 95% to 105%, 85% to 100%, 90% to It has a flexural strength retention of 100%, 95%-100%, 85%-99%, 90%-99%, or 95%-99%. In some embodiments, the polymer composition (PC) has a flexural strength of at least 120 MPa, at least 130 MPa, at least 140, or at least 150 MPa after aging in saline solution. In some embodiments, the polymer composition (PC) has a flexural strength of 180 MPa or less, 170 MPa or less, or 160 MPa or less after aging in saline solution. In some embodiments, the polymer composition (PC) is 120 MPa to 180 MPa, 130 MPa to 180 MPa, 140 MPa to 180 MPa, 150 MPa to 180 MPa, 120 MPa to 170 MPa, 130 MPa to 170 MPa, 140 MPa to 170 MPa after aging in a saline solution. , 150-170 MPa, 120-160 MPa, 130-160 MPa, 140-160 MPa, or 150-160 MPa. Flexural strength can be measured as described in the Examples section.

Polyamide (PA)
The polymer composition (PC) comprises polyamide (PA). Polyamide (PA) is a diamine component (A) containing (1) 20 mol % to 95 mol % of a C ₄ -C ₁₂ aliphatic diamine and 5 mol % to 80 mol % of a bis(aminoalkyl)cyclohexane; diamine component (A), the mole percentages of which are relative to the total moles of each diamine monomer in the diamine component; (2) 30 to 100 mole percent terephthalic acid and 0 to 70 mole percent %, preferably from 1 mol % to 70 mol % of cyclohexanedicarboxylic acid, these mol % relative to the total number of moles of each dicarboxylic acid monomer in the dicarboxylic acid component. derived from the polycondensation of monomers in a reaction mixture containing certain dicarboxylic acid components (B); Surprisingly, however, the incorporation of bis(aminoalkyl)cyclohexanes, or specific combinations of bis(aminoalkyl)cyclohexanes and cyclohexanedicarboxylic acids, into semi-aromatic polyamides improved mechanical properties after aging (e.g. tensile It has been found that impact-improved polymer compositions (PC) with improved retention of strength and flexural strength are obtained. Polyamides described herein have a glass transition temperature (“Tg”) of at least 145° C., a melting temperature (“Tm”) of at least 295° C., and a heat of fusion (“ΔH _f ”) of at least 30 J/g. .

Diamine component (A)
Diamine component (A) includes all diamines in the reaction mixture, including 20 mol% to 95 mol% _C4 -C12 _aliphatic diamines and 5 mol% to 80 mol% bis(aminoalkyl)cyclohexane is included. When referring to concentrations of monomers in diamine component (A), it is understood that concentrations are relative to total moles of all diamines in diamine component (A) unless otherwise specified.

In some embodiments, the _C4 - _C12 aliphatic diamine is represented by the formula:
H ₂ N—R ₁ —NH ₂ (1)
(wherein R′ ₁ is a C ₄ -C ₁₂ alkyl group, preferably a C ₆ -C ₁₀ alkyl group). In some embodiments, the _C4 - _C12 aliphatic diamines are 1,4-diaminobutane (putrescine), 1,5-diaminopentane (cadaverine), 2-methyl-1,5-diaminopentane, hexamethylene Diamine (or 1,6-diaminohexane), 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine , 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl- It is selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Preferably, the _C4 - _C12 aliphatic diamine is 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine , 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, and 1,10-diaminodecane. Preferably, the _C4 - _C12 aliphatic diamine is a _C5 - _C10 aliphatic diamine or a _C5 - _C9 aliphatic diamine. Most preferably, the _C4 - _C12 aliphatic diamine is 1,6-diaminohexane.

In some embodiments, the concentration of _C6 - _C12 aliphatic diamine is 25 mol% to 95 mol%, 30 mol% to 95 mol%, 35 mol% to 95 mol%, 40 mol% to 95 mol% , 45 mol % to 95 mol %, or 50 mol % to 95 mol %. In some embodiments, the concentration of C ₆ -C ₁₂ diamine is 20 mol % to 90 mol %, 25 mol % to 90 mol %, 30 mol % to 90 mol %, 35 mol % to 90 mol %, 40 mol % to 90 mol %, 45 mol % to 90 mol %, or 50 mol % to 90 mol %.

（式中、Ｒ_２及びＲ_３はＣ_１～Ｃ_１０アルキルから独立して選択され；Ｒ_ｉは、各位置において、アルキル、アリール、アルカリ又はアルカリ土類金属スルホン酸塩、アルキルスルホン酸塩、及び四級アンモニウムからなる群から選択され；ｉは０～１０の整数である）。－Ｒ_３－ＮＨ_２基は、メタ位（１，３－）又はパラ位（１，４－）に相対的に配置される。好ましくは、ｉは０であり、Ｒ_２及びＲ_３は共に－ＣＨ_２－である。最も好ましくは、ビス（アミノアルキル）シクロヘキサンは、１，３－ビス（アミノメチル）シクロヘキサン（「１，３－ＢＡＣ」）及び１，４－ビス（アミノメチル）シクロヘキサン（「１，４－ＢＡＣ」）から選択される。当然、ビス（アミノアルキル）シクロヘキサンはシス配座であってもトランス配座であってもよい。したがって、ジアミン成分（Ａ）は、シス－ビス（アミノアルキル）シクロヘキサンのみ、トランス－ビス（アミノアルキル）シクロヘキサンのみ、又はシス－とトランス－のビス（アミノアルキル）シクロヘキサンの混合物を含むことができる。 Bis(aminoalkyl)cyclohexane is represented by the formula:

(wherein R ₂ and R ₃ are independently selected from C ₁ -C ₁₀ alkyl; R _i is at each position alkyl, aryl, alkali or alkaline earth metal sulfonate, alkyl sulfonate, and quaternary ammonium; i is an integer from 0 to 10). The —R ₃ —NH ₂ groups are relatively positioned at the meta (1,3-) or para (1,4-) positions. Preferably i is 0 and both R ₂ and R ₃ are -CH ₂ -. Most preferably, the bis(aminoalkyl)cyclohexanes are 1,3-bis(aminomethyl)cyclohexane (“1,3-BAC”) and 1,4-bis(aminomethyl)cyclohexane (“1,4-BAC”). ). Of course, the bis(aminoalkyl)cyclohexane can be in cis or trans configuration. Thus, diamine component (A) can comprise only cis-bis(aminoalkyl)cyclohexanes, only trans-bis(aminoalkyl)cyclohexanes, or a mixture of cis- and trans-bis(aminoalkyl)cyclohexanes.

In some embodiments, the concentration of bis(aminoalkyl)cyclohexane is 5 mol% to 75 mol%, 5 mol% to 70 mol%, 5 mol% to 65 mol%, 5 mol% to 60 mol%, 5 mol % to 55 mol %, or 5 mol % to 50 mol %. In some embodiments, the concentration of bis(aminoalkyl)cyclohexane is 10 mol% to 75 mol%, 10 mol% to 70 mol%, 10 mol% to 65 mol%, 10 mol% to 60 mol%, 10 mol % to 55 mol %, or 10 mol % to 50 mol %, or 20 mol % to 40 mol %.

As noted above, in some embodiments, diamine component (A) comprises one or more additional diamines. Additional diamines are different from _C4 - _C12 aliphatic diamines and different from bis(aminoalkyl)cyclohexanes. In some embodiments, one, more, or all of the additional diamines are represented by Formula (1), each different from each other and different from the C ₄ -C ₁₂ aliphatic diamine. In some embodiments, each additional diamine is 1,2 diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3 diaminobutane, 1,4-diaminobutane, 1, 5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,5 dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7 tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1 ,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-bis (Aminomethyl)tetrahydrofuran, and N,N-bis(3-aminopropyl)methylamine. Also included in this category are cycloaliphatic diamines such as isophoronediamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis-p-aminocyclohexylmethane. In some embodiments, the diamine component does not include cycloaliphatic diamines other than bis(aminoalkyl)cyclohexanes. As used herein, free of monomer (e.g. bis(aminoalkyl)cyclohexane) means that the concentration of monomer in the corresponding component (e.g. diamine component (A)) is less than 1 mol%, preferably less than 0.5 mol. %, more preferably less than 0.1 mol %, more preferably less than 0.05 mol %, most preferably less than 0.01 mol %.

Dicarboxylic acid component (B)
The dicarboxylic acid component (B) contains 30 mol % to 100 mol % of terephthalic acid and 0 mol % to 70 mol %, preferably 1 mol % to 70 mol % of cyclohexanedicarboxylic acid, in the reaction mixture. of dicarboxylic acids. When referring to concentrations of monomers in the dicarboxylic acid component (B), it is understood that concentrations are relative to the number of moles of all dicarboxylic acids in the dicarboxylic acid component (A) unless otherwise specified. would be

In some embodiments, the concentration of terephthalic acid is from 35 mol % to 100 mol %, from 35 mol % to 100 mol %, from 40 mol % to 100 mol %, from 45 mol % to 100 mol %, or from 50 mol % to 100 moles. In some embodiments, the concentration of terephthalic acid is from 30 mol % to 99 mol %, from 35 mol % to 99 mol %, from 40 mol % to 99 mol %, from 45 mol % to 99 mol %, or from 50 mol % to 99 mol. In some embodiments, the concentration of terephthalic acid is 30 mol% to 95 mol%, 35 mol% to 97 mol%, 40 mol% to 97 mol%, 45 mol% to 97 mol%, or 50 mol% to 97 mol%. Mole.

（式中、Ｒ_ｊは、アルキル、アリール、アルカリ又はアルカリ土類金属スルホン酸塩、アルキルスルホン酸塩、及び四級アンモニウムからなる群から選択され；ｊは０～１０の整数である）。明示的な－ＣＯＯＨ基は、メタ位（１，３－）又はパラ位（１，４－）、好ましくはパラ位に相対的に配置される。好ましくは、シクロヘキサンジカルボン酸は、１，４－シクロヘキサンジカルボン酸（「ＣＨＤＡ」）（ｊは０である）である。当然、シクロヘキサンジカルボン酸は、シス配座であってもトランス配座であってもよい。したがって、ジカルボン酸成分（Ｂ）は、シス－シクロヘキサンジカルボン酸のみ、トランス－シクロヘキサンジカルボン酸のみ、又はシス－とトランス－のシクロヘキサンジカルボン酸の混合物を含むことができる。 Cyclohexanedicarboxylic acid is represented by the formula:

(wherein R _j is selected from the group consisting of alkyl, aryl, alkali or alkaline earth metal sulfonates, alkyl sulfonates, and quaternary ammonium; j is an integer from 0-10). Explicit -COOH groups are relatively positioned in the meta (1,3-) or para (1,4-) positions, preferably in the para position. Preferably, the cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid (“CHDA”) (where j is 0). Naturally, the cyclohexanedicarboxylic acid can be in the cis or trans configuration. Thus, the dicarboxylic acid component (B) can comprise only cis-cyclohexanedicarboxylic acid, only trans-cyclohexanedicarboxylic acid, or a mixture of cis- and trans-cyclohexanedicarboxylic acids.

In some embodiments, the concentration of cyclohexanedicarboxylic acid is 1 mol% to 70 mol%, 1 mol% to 65 mol%, 1 mol% to 60 mol%, 1 mol% to 55 mol%, or 1 mol% ~50 mol%.

As noted above, in some embodiments, dicarboxylic acid component (B) comprises one or more additional dicarboxylic acids. Each additional dicarboxylic acid is different from each other and different from terephthalic acid and cyclohexanedicarboxylic acid. In some embodiments, one, more, or all of the additional dicarboxylic acids are represented by Formula (3), each different from each other and different from cyclohexanedicarboxylic acid.

In some embodiments, the one or more additional dicarboxylic acids are independently selected from the group consisting of _C4 - _C12 aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids. Examples of desirable _C4 - _C10 aliphatic dicarboxylic acids include, but are not limited to, succinic acid [HOOC-( _CH2 ) ₂ -COOH], glutaric acid [HOOC-( _CH2 ) ₃ -COOH], 2,2-dimethyl-glutaric acid [HOOC-C(CH ₃ ) ₂ -(CH ₂ ) ₂ -COOH], adipic acid [HOOC-(CH ₂ ) ₄ -COOH], 2,4,4-trimethyl-adipine acid [HOOC-CH( _CH3 ) _-CH2 -C( _CH3 ) _2- CH2 _- COOH], pimelic acid [HOOC-( _CH2 ) ₅ -COOH], suberic acid [HOOC-( _CH2 ) ₆ -COOH], azelaic acid [HOOC-(CH ₂ ) ₇ -COOH], sebacic acid [HOOC-(CH ₂ ) ₈ -COOH], 1,12-dodecanedioic acid [HOOC-(CH ₂ ) ₁₀ -COOH] is mentioned.

Examples of desirable aromatic dicarboxylic acids include, but are not limited to, phthalic acids such as isophthalic acid (IA), naphthalenedicarboxylic acids (eg naphthalene-2,6-dicarboxylic acid), 4,4'bibenzoic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoro Propane, 2,2-bis(4-carboxyphenyl)ketone, 4,4′-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3- carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene.

Examples of desirable cycloaliphatic dicarboxylic acids include, but are not limited to, cyclopropane-1,2-dicarboxylic acid, 1-methylcyclopropane-1,2-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid and 1,3-adamantanedicarboxylic acid.

In some embodiments in which the polyamide (PA) comprises one or more additional dicarboxylic acids, the total concentration of one or more additional dicarboxylic acids is 20 mol% or less.

を含み、更に、ジカルボン酸成分（Ｂ）中にシクロヘキサンジカルボン酸が存在する場合には、それぞれ以下の式で表される繰り返し単位Ｒ_ＰＡ３及びＲ_ＰＡ４：

（式中、Ｒ_１～Ｒ_３、Ｒ_ｉ、Ｒ_ｊ、ｉ、及びｊは、上で定義した通りである）を含む。当業者であれば、繰り返し単位Ｒ_ＰＡ１がＣ_４～Ｃ_１２脂肪族ジアミンとテレフタル酸との重縮合から形成され、繰り返し単位Ｒ_ＰＡ３がＣ_４～Ｃ_１２脂肪族ジアミンとシクロヘキサンジカルボン酸との重縮合から形成され、繰り返し単位Ｒ_ＰＡ２がビス（アミノアルキル）シクロヘキサンとテレフタル酸との重縮合から形成され、繰り返し単位Ｒ_ＰＡ４がビス（アミノアルキル）シクロヘキサンとシクロヘキサンジカルボン酸との重縮合から形成されることを認識するであろう。いくつかの実施形態では、Ｒ_１は－（ＣＨ_２）－_ｍであり、式中のｍは５～１０、好ましくは５～９、最も好ましくは６である。加えて、又は代わりに、いくつかの実施形態では、Ｒ_２及びＲ_３は共に－ＣＨ_２－であり、ｉ及びｊは共にゼロである。いくつかの実施形態では、ビス（アミンアルキル）シクロヘキサンは１，３－ビス（アミノメチル）シクロヘキサンであり、シクロヘキサンジカルボン酸は１，４－シクロヘキサンジカルボン酸である。 Repeating Units of Polyamide (PA) Polyamides (PA) formed from the polycondensation of monomers in the above-described diamine component and dicarboxylic acid component are repeating units R _PA1 and R _PA2 represented by the following formulas, respectively:

and further, when cyclohexanedicarboxylic acid is present in the dicarboxylic acid component (B), repeating units R _PA3 and R _PA4 respectively represented by the following formulas:

wherein R ₁ -R ₃ , R _i , R _j , i, and j are as defined above. Those skilled in the art will appreciate that the repeating unit R _PA1 is formed from the polycondensation of a C ₄ -C ₁₂ aliphatic diamine and terephthalic acid, and the repeating unit R _PA3 is the polymerization of a C ₄ -C ₁₂ aliphatic diamine and cyclohexanedicarboxylic acid. condensation, with repeat unit _RPA2 formed from the polycondensation of bis(aminoalkyl)cyclohexane and terephthalic acid, and repeat unit _RPA4 formed from the polycondensation of bis(aminoalkyl)cyclohexane and cyclohexanedicarboxylic acid. will recognize that In some embodiments, R ₁ is -(CH ₂ )- _m , where m is 5-10, preferably 5-9, most preferably 6. Additionally or alternatively, in some embodiments, both R ₂ and R ₃ are —CH ₂ — and i and j are both zero. In some embodiments, the bis(aminealkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane and the cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

In some embodiments, the total concentration of repeat units R _PA1 and R _PA2 is at least 50 mol %, at least 60 mol %, at least 70 mol %, at least 80 mol %, at least 90 mol %, at least 95 mol %, at least 97 mol %, at least 98 mol %, at least 99 mol %, or at least 99.5 mol %. In some embodiments where an optional cyclohexanedicarboxylic acid is present in dicarboxylic acid component (B), the total concentration of repeat units R _PA1 -R _PA4 is at least 50 mol %, at least 60 mol %, at least 70 mol %, at least 80 mol %, at least 90 mol %, at least 95 mol %, at least 97 mol %, at least 98 mol %, at least 99 mol %, or at least 99.5 mol %. It will be understood that when referring to mol % of repeat units, the concentrations are relative to the total number of repeat units in the indicated polymer unless otherwise specified.

Polyamide (PA) is a semi-crystalline polyamide. As used herein, a semi-crystalline polyamide is a polyamide having a heat of fusion (“ΔH _f ”) of at least 5 joules per gram (“J/g”). In some embodiments, the polyamides (PA) described herein have a ΔH _f of at least 30 J/g, or at least 35 J/g. Additionally or alternatively, in some embodiments, the polyamide (PA) has a ΔH _f of 60 J/g or less, or 55 J/g or less. In some embodiments, the polyamide (PA) has a ΔH _f of 30 J/g to 60 J/g or 35 J/g to 60 J/g, 30 J/g to 55 J/g, or 35 J/g to 55 J/g . ΔH _f can be measured according to ASTM D3418 using a heating rate of 20° C./min.

The polyamide (PA) has a Tg of at least 145°C, preferably at least 150°C. In some embodiments, the polyamide (PA) has a Tg of 190°C or less, 180°C or less, or 170°C or less. In some embodiments, the polyamide (PA) is a have a Tg. Tg can be measured according to ASTM D3418.

The polyamide (PA) has a Tm of at least 295°C, preferably at least 300°C. In some embodiments, the polyamide (PA) has a Tm of 360°C or less, 350°C or less, or 340°C or less. In some embodiments, the polyamide (PA) is a have a Tm. Tm can be measured according to ASTM D3418.

In some embodiments, the polyamide (PA) is 1,000 g/mole to 40,000 g/mole, such as 2,000 g/mole to 35,000 g/mole, 4,000 to 30,000 g/mole, or 5 ,000 g/mole to 20,000 g/mole. Number average molecular weight Mn can be measured by gel permeation chromatography (GPC) using ASTM D5296 using polystyrene standards.

The polyamides (PA) described herein can be prepared by any conventional method adapted for synthesizing polyamides and polyphthalamides. Preferably, the polyamide (PA) is melted in the presence of less than 60% by weight, preferentially less than 50% by weight of water, to a temperature of at least Tm + 10°C (Tm is the melting temperature of polyamide (PA)). It is prepared by reacting (by heating) and the weight percentages here are relative to the total weight of the reaction mixture.

The polyamides (PA) described herein can be prepared, for example, by thermal polycondensation (also called polycondensation or condensation) of aqueous solutions of monomers and comonomers. In one embodiment, the polyamide (PA) is present in the reaction mixture at least in the _C4 - _C12 aliphatic diamine, bis(aminoalkyl)cyclohexane, terephthalic acid, and dicarboxylic acid component (B). is formed by reacting with cyclohexanedicarboxylic acid. In some embodiments, the total number of moles of diamines in the reaction mixture is substantially equimolar to the total number of moles of dicarboxylic acids in the reaction mixture. As used herein, substantially equimolar means a value that is ±15% of the indicated number of moles. For example, relative to the concentrations of diamine and dicarboxylic acid in the reaction mixture, the total moles of diamine in the reaction mixture is ±15% of the total moles of dicarboxylic acid in the reaction mixture. Polyamide (PA) is a monofunctional molecule that can react with amine or carboxylic acid moieties and may contain chain limiters used to control the molecular weight of polyamide (PA). For example, the chain limiter can be acetic acid, propionic acid, benzoic acid and/or benzylamine. Catalysts can also be used. Examples of catalysts are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites such as sodium hypophosphite and phenylphosphinic acid. Stabilizers such as phosphites may also be used.

Polymer composition (PC)
A polymer composition (PC) comprises a polyamide (PA) and a reactive impact modifier. In some embodiments, the polymer composition can include one or more optional ingredients selected from the group consisting of reinforcing agents and additives. Additives include, but are not limited to, impact modifiers, plasticizers, colorants, pigments (e.g. black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g. density polyethylene, calcium stearate, magnesium stearate, or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, acid scavengers, and other processing aids.

In some embodiments, the polyamide (PA) concentration in the polymer composition (PC) is at least 5 wt% or at least 10 wt%. In some embodiments, the polyamide (PA) concentration in the polymer composition (PC) is 80 wt% or less, or 70 wt% or less. In some embodiments, the polyamide (PA) concentration in the polymer composition (PC) is 5 wt% to 80 wt%, or 10 wt% to 70 wt%.

The polymer composition (PC) contains a reactive impact modifier (IM). Impact modifiers generally have a low Tg, eg, a Tg below room temperature, below 0°C, or even below -25°C. As a result of their low Tg, tougheners are typically elastomers at room temperature. The polymeric backbone of the impact modifier is an elastomeric backbone comprising polyethylene and copolymers thereof, such as terpolymers of ethylene, acrylic acid esters and glycidyl methacrylate; copolymers of ethylene and butyl ester acrylate; ethylene and butyl ester acrylate; Ethylene-maleic anhydride copolymers; Ethylene-butene; Ethylene-hexene; Ethylene-octene; Polypropylene and its copolymers; Rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene ethylene butadiene styrene (SEBS) block copolymer styrene butadiene styrene (SBS); methacrylate-butadiene-styrene (MBS) type core-shell elastomers, or mixtures of one or more of the above.

Reactive impact modifiers (IM) are functionalized impact modifiers. Molecules that functionalize the impact modifier include groups that react with the polyamide to form covalent bonds. In some embodiments, this group reacts with amine groups on the polyamide. Reactive impact modifiers (IMs) can be formed by copolymerization of monomers containing functionalization or by grafting the backbone of the impact modifier with functionalized molecules. In some embodiments, the impact modifier is anhydride, carboxyl, acrylate, epoxy, amino, or vinyl functionalized.

In some embodiments, the reactive impact modifier (IM) is a terpolymer of ethylene, acrylic ester and glycidyl methacrylate; a copolymer of ethylene and butyl ester acrylate; a copolymer of ethylene, butyl ester acrylate and glycidyl methacrylate. EPR Functionalized with Maleic Anhydride; Styrene Copolymer Functionalized with Maleic Anhydride; EPDM Functionalized with Maleic Anhydride, SEBS Copolymer with Maleic Anhydride Functionalized styrene-acrylonitrile copolymers functionalized with maleic anhydride; ABS copolymers functionalized with maleic anhydride. Alternatively, the reactive impact modifier can be selected from any of the previous lists functionalized with epoxides instead of maleic anhydride. Excellent results were obtained with SEBS copolymers grafted with maleic anhydride.

In some embodiments, the reinforcing agent concentration in the polymer composition (PC) is at least 1 wt%, at least 2 wt%, or at least 3 wt%. In some embodiments, the toughener concentration in the polymer composition (PC) is 20 wt% or less, 15 wt% or less, or 10 wt% or less. In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is 1 wt% to 20 wt%, 2 wt% to 15 wt%, or 3 wt% to 10 wt%.

In some embodiments, the polymer composition (PC) includes reinforcing agents. A wide variety of reinforcing agents, also called reinforcing fibers or fillers, can be added to the polymer composition (PC). In some embodiments, reinforcing agents include mineral fillers (including but not limited to talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymer fibers, selected from aramid fibres, aluminum fibres, titanium fibres, magnesium fibres, boron carbide fibres, rock wool fibres, steel fibres, and wollastonite.

Generally, the reinforcing agent is a fibrous reinforcing agent or a particulate reinforcing agent. A fibrous reinforcement refers to a material having a length, width and thickness where the average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio of at least 5, at least 10, at least 20 or at least 50, defined as the average ratio between the length and the largest of the width and thickness. In some embodiments, fibrous reinforcing agents (eg, glass fibers or carbon fibers) have an average length of 3 mm to 50 mm. In some such embodiments, the fibrous reinforcement has an average length of 3 mm to 10 mm, 3 mm to 8 mm, 3 mm to 6 mm, or 3 mm to 5 mm. In alternative embodiments, the fibrous reinforcement has an average length of 10 mm to 50 mm, 10 mm to 45 mm, 10 mm to 35 mm, 10 mm to 30 mm, 10 mm to 25 mm or 15 mm to 25 mm. The average length of the fibrous reinforcing agent can be interpreted as the average length of the fibrous reinforcing agent before incorporation into the polymer composition (PC), or the average length of the fibrous reinforcing agent in the polymer composition (PC). It can be interpreted as the average length.

Among the fibrous reinforcing agents, glass fibers are preferred. Glass fibers are silica-based glass compounds containing several metal oxides that can be tailored to yield different types of glass. The predominant oxide is silica in the form of silica sand, and other oxides such as calcium, sodium and aluminum are incorporated to lower the melting temperature and prevent crystallization. Glass fibers can be added as endless fibers or chopped glass fibers. The glass fibers generally have an equivalent diameter of 5-20, preferably 5-15 μm, more preferably 5-10 μm. All of the glass fiber types, such as A, C, D, E, M, S, R, T glass fibers (described in Additives for Plastics Handbook, 2nd ed, John Murphy, chapter 5.2.3, pages 43-48). or any mixture thereof or mixtures thereof.

E, R, S and T glass fibers are well known in the art. They are described, inter alia, in Fiberglass and Glass Technology, Wallenberger, Frederick T.; Bingham, Paul A.; (Eds.), 2010, XIV, chapter 5, pages 197-225. R, S and T glass fibers consist essentially of oxides of silicon, aluminum and magnesium. In particular, those glass fibers typically contain 62-75% by weight SiO2, 16-28% by weight Al2O3 and 5-14% by weight MgO. On the other hand, R, S and T glass fibers contain less than 10 wt% CaO.

In some embodiments, the glass fibers are high modulus glass fibers. The high modulus glass fibers have a modulus of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa as measured according to ASTM D2343. Examples of high modulus glass fibers include, but are not limited to, S, R and T glass fibers. Commercial sources of high modulus glass fibers are S-1 and S-2 glass fibers provided by Taishan and AGY, respectively.

The morphology of glass fibers is not particularly limited. As noted above, the glass fibers may have a circular cross-section (“round glass fibers”) or a non-circular cross-section (“flat glass fibers”). Non-limiting examples of suitable flattened glass fibers include glass fibers having oval, elliptical and rectangular cross-sections. In some embodiments where the polymer composition comprises flat glass fibers, the longest cross-sectional diameter of the flat glass fibers is at least 15 μm, preferably at least 20 μm, more preferably at least 22 μm, even more preferably at least 25 μm. Additionally or alternatively, in some embodiments, the longest cross-sectional diameter of the flat glass fibers is at most 40 μm, preferably at most 35 μm, more preferably at most 32 μm, even more preferably at most 30 μm. In some embodiments, the flat glass fibers have a cross-sectional diameter in the range of 15-35 μm, preferably 20-30 μm, more preferably 25-29 μm. In some embodiments, the shortest cross-sectional diameter of the flat glass fibers is at least 4 μm, preferably at least 5 μm, more preferably at least 6 μm, even more preferably at least 7 μm. Additionally or alternatively, in some embodiments, the shortest cross-sectional diameter of the flat glass fibers is at most 25 μm, preferably at most 20 μm, more preferably at most 17 μm, even more preferably at most 15 μm. In some embodiments, the shortest cross-sectional diameter of the flat glass fibers is in the range of 5-20 μm, preferably 5-15 μm, more preferably 7-11 μm.

In some embodiments, the flat glass fibers have an aspect ratio of at least 2, preferably at least 2.2, more preferably at least 2.4, and even more preferably at least 3. Aspect ratio is defined as the ratio of the longest diameter in a cross-section of a glass fiber to the shortest diameter in the same cross-section. Additionally or alternatively, in some embodiments, the flat glass fibers have an aspect ratio of at most 8, preferably at most 6, more preferably at most 4. In some embodiments, the flat glass fibers have an aspect ratio of 2-6, preferably 2.2-4. In some embodiments in which the glass fibers are round glass fibers, the aspect ratio of the glass fibers is less than 2, preferably less than 1.5, more preferably less than 1.2, even more preferably less than 1.1, most It is preferably less than 1.05. Of course, those skilled in the art will understand that regardless of the glass fiber morphology (eg, circular or flat), by definition the aspect ratio cannot be less than one.

In some embodiments, the concentration of reinforcing agent (e.g., glass or carbon fiber) in the polymer composition (PC) is at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt% . In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is 70 wt% or less, 65 wt% or less, or 60 wt% or less. In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is from 5 wt% to 70 wt%, from 10 wt% to 70 wt%, from 10 wt% to 65 wt%, from 10 wt% to 60 wt%. % by weight, 15% to 60% by weight, or 20% to 60% by weight.

（式中、Ｒ_１、Ｒ_２は、同一であるか若しくは異なり、Ｒ_１及びＲ_２のそれぞれは、水素又は直鎖若しくは分岐Ｃ_１～Ｃ_６アルキル基若しくはアリール基であり；Ｒ_３は、直鎖若しくは分岐Ｃ_１～Ｃ_１０アルキレン基、Ｃ_６～Ｃ_１０アリーレン基、アルキル－アリーレン基、又はアリール－アルキレン基であり；Ｍは、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、チタンイオン、及びそれらの組み合わせから選択され；ｍは、２又は３の整数であり；ｎは、１又は３の整数であり；ｘは、１又は２の整数である）。 In some embodiments, the halogen-free flame retardant is an organophosphorus compound selected from the group consisting of phosphine salts (phosphinates), diphosphine salts (diphosphinates), and condensation products thereof. Preferably, the organophosphorus compound is selected from the group consisting of phosphinates of formula (I), diphosphinates of formula (II) and condensation products thereof:

(wherein R ₁ and R ₂ are the same or different, each of R ₁ and R ₂ is hydrogen or a linear or branched C ₁ -C ₆ alkyl or aryl group; R ₃ is linear or branched C ₁ -C ₁₀ alkylene group, C ₆ -C ₁₀ arylene group, alkyl-arylene group, or aryl-alkylene group; M is calcium ion, magnesium ion, aluminum ion, zinc ion, titanium ion , and combinations thereof; m is an integer of 2 or 3; n is an integer of 1 or 3; x is an integer of 1 or 2).

Preferably, R ₁ and R ₂ are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and phenyl; R3 is methylene, ethylene, n -propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene , phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene; M is selected from aluminum and zinc ions.

Phosphinates are preferred as organophosphorus compounds. Suitable phosphinates are described in US Pat. No. 6,365,071, which is incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinate, calcium phosphinate and zinc phosphinate. Excellent results were obtained with aluminum phosphinate. Among the aluminum phosphinates, aluminum ethylmethylphosphinate and aluminum diethylphosphinate and combinations thereof are preferred.

In some embodiments, the polymer composition (PC) further comprises an acid scavenger, most desirably in embodiments where halogen-free flame retardants are formulated. Acid scavengers include, but are not limited to, silicone; silica; boehmite; aluminum oxide, calcium oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, oxide Metal oxides such as bismuth, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, and tungsten oxide; aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, metal powders such as copper and tungsten; and metal salts such as barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. In some embodiments where the polymer composition (PC) comprises an acid scavenger, the concentration of acid scavenger is 0.01 wt% to 5 wt%, 0.05 wt% to 4 wt%, 0.08 wt% % to 3 wt%, 0.1 wt% to 2 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.5 wt%, or 0.1 wt% to 0.3 wt% is.

In some embodiments, the total additive concentration in the polymer composition (PC) is at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt%. In some embodiments, the total additive concentration in the polymer composition (PC) is 20 wt% or less, 15 wt% or less, 10 wt% or less, 7 wt% or less, or 5 wt% or less. In some embodiments, the total additive concentration in the polymer composition (PC) is 0.1 wt% to 20 wt%, 0.1 wt% to 15 wt%, 0.1 wt% to 10 wt% , 0.2% to 7% by weight, or 0.3% to 5% by weight.

In some embodiments, the polymer composition (PC) further comprises one or more additional polymers. In some such embodiments, at least one of the additional polymers is a semi-crystalline or amorphous polyamide, such as an aliphatic polyamide or a semi-aromatic polyamide, more typically an aromatic or aliphatic saturated These are polyamides obtained by polycondensation between diacids and aliphatic saturated or aromatic primary diamines, polycondensation of lactams, amino acids or mixtures of these different monomers.

Preparation of Polymer Composition (PC) The present invention further relates to a method of producing a polymer composition (PC). The method includes melt blending a polyamide (PA) reactive impact modifier (IM) and any optional ingredients (eg, reinforcing agents).

Any melt-blending method can be used to mix the polymeric and non-polymeric components associated with the present invention. For example, the polymeric components and non-polymeric components can be fed into a single or twin screw extruder, an agitator, a single or twin screw kneader, or a melt mixer such as a Banbury mixer, and the step of adding , simultaneous addition of all ingredients or batch-wise stepwise addition. When the polymeric and non-polymeric ingredients are added batchwise and gradually, a portion of the polymeric and/or non-polymeric ingredients is added first and then added thereafter until a well-mixed composition is obtained. It is melt mixed with the remaining polymeric and non-polymeric raw materials to be used. Stretch extrusion or pultrusion may be used to prepare the reinforced composition when the reinforcing agent exhibits long physical shapes such as long glass fibers and continuous fibers.

Articles and Uses The present invention also relates to articles comprising the polymer composition (PC). Due, at least in part, to improved mechanical retention after aging in aqueous polyol or saline solutions, the polymer compositions (PCs) desirably are exposed to elevated temperatures and aqueous polyol or saline solutions during their intended use. It is incorporated into any article that will be exposed to aqueous solutions.

In some embodiments, the article is selected from the group consisting of automotive parts, marine parts, and aerospace parts. In some embodiments, the article is selected from the group consisting of fluid inlet/outlet ports, fluid inlet/outlet valves, fluid pump housings, fluid pump impellers, fluid hose connectors, fluid hoses, fluid reservoirs, and fluid valves; The fluid is an aqueous polyol solution, preferably an aqueous solution of ethylene glycol, propylene glycol, or diethylene glycol. The polymer composition (PC) is further advantageously incorporated into such articles when such articles are used in engine compartments (eg when exposed to high temperatures).

In some embodiments, the article is selected from subsurface and subsea oil and gas components. In some embodiments, the article is selected from sucker rod guides or other polymer-based components in artificial lift systems. The sucker rod guide can be overmolded onto the sucker rod, glued to the sucker rod, or a snap-on design that is installed in the field.

In some embodiments, articles are formed from the polymer composition (PC) by any process suitable for thermoplastics, such as extrusion, injection molding, blow molding, rotational molding or compression molding. Polymer composition (C) can also be used in overmolding preformed shapes to build hybrid structures.

In some embodiments, the article is from the polymer composition (PC), e.g., in the form of filaments, by a process involving extrusion of the polymer composition (PC), or in this case in powder form. Printed by a process that includes the step of laser sintering of a polymer composition (PC).

The present invention is a method of manufacturing three-dimensional (3D) objects in an additive manufacturing system comprising the steps of providing a part material comprising a polymer composition (PC) and printing layers of the three-dimensional object from the part material. It also relates to a method comprising

Thus, the polymer composition (PC) can be in the form of threads or filaments used in the process of 3D printing, such as fused filament manufacturing, also known as Fused Deposition Modeling (“FDM”).

The polymer composition (PC) can also be in the form of a powder, such as a substantially spherical powder, used in processes of 3D printing, such as selective laser sintering (“SLS”).

Use of Polymer Compositions (PC) and Articles The present invention relates to the use of polymer compositions (PC) or articles for manufacturing automotive, marine or aerospace parts as described above. The present invention also relates to the use of the polymer composition (PC) or articles for making articles used in oil and gas recovery as described above. The invention also relates to the use of the polymer composition (PC) for 3D printing objects.

This example demonstrates the synthesis, thermal performance, and mechanical performance of polyamides.

The raw materials used to form the samples are as follows:
Polyamide 1 (“PA1”): PA 6, T/1,3-BAC, T/6, CHDA/1,3-BAC, CHDA (Tg=165° C. and Tm=330° C.), synthesized from :
- Hexamethylenediamine (70% by weight, from Ascend Performance Materials)
- 1,3-bis(aminomethyl)cyclohexane (from Mitsubishi Gas Chemical Company)
- terephthalic acid (from Flint Hills Resources)
- 1,4-cyclohexanedicarboxylic acid (from Eastman Chemical Company)
- Polyamide 2 ("PA2"): PA 6T/66 (65/35) (from Solvay Specialty Polymers USA, L.L.C.); Tg 100C
- Polyamide 3 ("PA3"): PA 6T/6I (70/30) (from Solvay Specialty Polymers USA, L.L.C.); Tg 135C
- Polyamide 4 ("PA4"): PA 6T/6I/66 (65/25/10) (from Solvay Specialty Polymers USA, L.L.C.); Tg 125C
- Reactive Impact Modifier ("IM"): maleic anhydride functionalized SEBS copolymer (Kraton's KratonTM FG 1901 GT)
- Stabilizer package: a mixture of CuI/KI and an organic antioxidant (thermal stabilizer) - Nucleating agent: Talc (Mistron Vapor, from Imerys)
• Pigment: Black pigment. Carbon black release agent/lubricant: Polyethylene release agent/lubricant Glass fiber 1 (“GF1”): Chopped-E glass fiber (OCV ^TM 983, from Owens Corning)
Glass fiber 2 (“GF2”): Chopped-E glass fiber (NEG HP 3610, from Nippon Electric Glass Co.)
• Glass Fiber 3 ("GF3"): Chopped-E glass fiber (NEG HP 3540, from Nippon Electric Glass Co.).

Example 1 - Synthesis of PA1 This example demonstrates the synthesis of Polyamide 1.

PA1 was prepared in an autoclave reactor equipped with a distillation line fitted with a pressure control valve. A reactor was charged with 498 g of 70% hexamethylenediamine, 165 g of 1,3-bis(aminomethyl)cyclohexane, 635 g of terephthalic acid, 20 g of 1,4-cyclohexanedicarboxylic acid, 355 g of deionized water, 7.2 g of Glacial acetic acid and 0.32 g of phosphoric acid were added. The reactor was sealed, purged with nitrogen and heated to 260°C. The generated water vapor was slowly released to maintain the internal pressure at 120 psig. The temperature was raised to 335°C. The reactor pressure was reduced to atmospheric pressure while the reaction mixture was held at 335° C. for 60 minutes. Polymer was removed from the reactor and used to prepare compound formulations.

Example 2 - Mechanical Performance This example demonstrates the mechanical performance of the polymer composition.

To demonstrate mechanical performance, polymer compositions were formed by melt blending polymer resins with various additives in an extruder. The polymer composition was then molded into a test sample and the test sample was aged in an aqueous polyol solution (immersing the test sample in a 50:50 ethylene glycol:water solution at 130°C for 1000 hours) or in a saline solution. Mechanical properties (tensile and flexural properties) were tested before (“as molded”) and after (“after aging”) aging (immersion of test samples in 26% NaCl aqueous solution at 130° C. for 1000 hours). Tensile strength was measured according to ISO 527-2 on dumbbell-shaped ISO Type 1A tensile specimens having the following nominal dimensions: total length 170 mm, gauge length 75 mm, parallel section length 80 mm, parallel section width 10 mm, The width of the grip part is 20mm and the thickness is 4mm. Flexural strength was measured according to ISO 178 on standard ISO flexural specimens with the following nominal dimensions: length 80 mm, width 10 mm, thickness 4 mm. Table 1 shows the sample parameters, Table 2 shows the results of tensile strength measurements after aging in aqueous polyol solution, and Table 3 shows the results of flexural strength measurements after aging in saline solution. In the tables, "E" stands for example and "CE" stands for counter-example. All values in Table 1 are reported in weight percent.

Referring to Table 2, samples containing PA1 surprisingly not only had increased retention of tensile strength after aging, but also increased tensile strength values compared to samples containing PA2 and PA4. bottom. For example, E1 has significantly improved tensile strength retention (also improved tensile strength after aging) compared to CE1 and CE2.

Referring to Table 3, the samples containing PA surprisingly had increased retention of flexural strength after thermal aging and had comparable or improved flexural strength. Similar to tensile strength, E1 had improved retention of flexural strength compared to CE3-CE7. Furthermore, after thermal aging, E1 had comparable flexural strength compared to CE-1 and improved flexural strength compared to CE4-CE7.

The above embodiments are intended to be illustrative, not limiting. Additional embodiments are within the concept of the present invention. Additionally, although the present invention has been described with reference to specific embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. deaf. Any incorporation by reference of documents above is limited such that no subject matter is incorporated that is contrary to the explicit disclosure herein.

Claims (15)

- a polyamide (PA);
- a reactive impact modifier (IM);
A polymer composition (PC) comprising
The polyamide (PA) is
- 20 mol% to 95 mol% of a _C4 - _C12 aliphatic diamine;
- 5 mol% to 80 mol% of a bis(aminoalkyl)cyclohexane;
wherein the mole percents are relative to the total moles of each diamine in said diamine component (A);
- 30 mol% to 100 mol% of terephthalic acid;
- 0 mol% to 70 mol% of cyclohexanedicarboxylic acid;
wherein the mole percentages of these are relative to the total number of moles of each dicarboxylic acid in said dicarboxylic acid component (B)
A polymer composition (PC) derived from the polycondensation of monomers in a reaction mixture comprising The C ₄ -C ₁₂ aliphatic diamines are 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2 ,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino Polymer composition (PC) according to claim 1, selected from the group consisting of undecane and 1,12-diaminododecane; preferably said _C4 - _C12 aliphatic diamine is 1,6-diaminohexane. Polymer composition (PC) according to claim 1 or 2, wherein the bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane. wherein said dicarboxylic acid component (B) contains 1 mol% to 70 mol% of cyclohexanedicarboxylic acid, preferably 1,4-cyclohexanedicarboxylic acid, relative to the total number of moles of each dicarboxylic acid in said carboxylic acid component; The polymer composition (PC) according to any one of Items 1-3. The polymer composition (PC ). Polymer composition (PA) according to any one of the preceding claims, wherein said reactive impact modifier (IM) is a maleic anhydride functionalized impact modifier. Polymer composition (PA) according to any one of the preceding claims, wherein the concentration of said reactive impact modifier (IM) is between 1% and 20% by weight. Polymer composition (PC) according to any one of the preceding claims, further comprising a halogen-free flame retardant. Polymer composition (PC) according to any one of the preceding claims, further comprising from 5% to 70% by weight of a reinforcing agent relative to the total weight of the polymer composition. Polymer composition (PC) according to claim 9, wherein the reinforcing agent is glass or carbon fibre, preferably glass fibre. 11. Any of claims 1-10, wherein the polymer composition (PC) has a tensile strength retention of at least 60% after aging in a 50:50 ethylene glycol:water solution at 130°C for 1000 hours. A polymer composition (PC) according to claim 1. 12. The polymer composition (PC) according to any one of the preceding claims, wherein the polymer composition (PC) has a flexural strength retention of at least 85% after 1000 hours of thermal aging in a 26 wt% aqueous NaCl solution at 130°C. of the polymer composition (PC). An article comprising the polymer composition (PC) according to any one of claims 1-12, which is an automobile part. An article comprising the polymer composition (PC) according to any one of claims 1 to 13, which is a constituent of underground or subsea oil and gas. A polymer composition according to any one of claims 1 to 12 or an article according to claims 13 or 14, wherein the polymer composition (PC) is in contact with an aqueous polyol solution or a saline solution.